POLYBROMINATED DIPHENYL ETHERS (BDES · shows that PBDEs can cause a wide range of effects, in...

PolyBDEs EQS dossier 2011

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POLYBROMINATED DIPHENYL ETHERS (BDES)

This EQS dossier was prepared by the Sub-Group on Review of the Priority Substances List (under Working Group E of the Common Implementation Strategy for the Water Framework Directive).

The dossier was reviewed by the Scientific Committee on Health and Environmental Risks (SCHER), which commented on a number of issues. In response, some amendments have been made and explanation added to the dossier.

Introduction

The substances “pentaBDE” and “octaBDE” have been prioritised through 2 consecutive prioritisation procedures: pentaBDE was prioritised following COMMPS1 (COmbined Monitoring-based and Modelling-based Priority Setting scheme) procedure in 2001, while octaBDE has recently been prioritised in the context of the second European Commission proposal for a new list of priority substances, for the reason that it is a PBT (Persistent, Bioaccumulative and Toxic) and a vPvB (very Persistent and very Bioaccumulative) substance. Following this latter prioritisation and the fact that pentaBDE EQS needed to be revised, it was decided to produce a unique fact sheet reporting a common EQS for all BDE congeners linked to c-pentaBDE and c-octaBDE, that is to say tetra- to nona-BDE congeners.

The polybrominated diphenyl ethers (polyBDE) are diphenyl ethers with degrees of bromination varying from 2 to 10 representing a list of 209 congeners (see section “Nomenclature of all 209 BDE congeners”, page 4). Among these polyBDEs which are mainly used as flame retardants, three are available commercially: “pentaBDE commercial product”, “octaBDE commercial product” and “decaBDE commercial product”. However, these products are all a mixtures of diphenyl ethers as shown in the table hereunder. Therefore, to differentiate “pentaBDE commercial product” and “octaBDE commercial product” from “pentaBDE substance” and “octaBDE substance”, respectively, these commercial products will be referred to as “c-pentaBDE” and “c-octaBDE” in the present fact sheet.

Commercial mixtures

Content (% w/w) of

Substance

c-PentaBDE c-OctaBDE

TriBDE (CAS 49690-94-0) 0 – 1

TetraBDE (CAS 40088-47-9) 24 – 38

PentaBDE (CAS 32534-81-9) 50 – 62 ≤ 0.5

HexaBDE (CAS 36483-60-0) 4 – 12 ≤ 12

HeptaBDE (CAS 68928-80-3) Trace ≤ 45

OctaBDE (CAS 32536-52-0) ≤ 33

NonaBDE (CAS 63936–56–1) ≤ 10

DecaBDE (CAS 1163-19-5) ≤ 0.7

As stated above, the present fact sheet addresses pentaBDE and the newly prioritised substance octaBDE for derivation of EQS values. However, the data on toxicity and ecotoxicity that are reported in the EU Risk Assessment Report all come from studies performed with the following commercial products: c-pentaBDE, c-octaBDE and c-decaBDE. DecaBDE was not prioritised along the prioritisation process. However, given the faculty of brominated diphenyl ether compound – including decaBDE – to degrade into lower brominated ones (UNEP, 2010),

1 Revised proposal for a list of priority substances in the context of the Water Framework Directive (COMMPS procedure). Fraunhofer-Institut, June 1999. Available at http://ec.europa.eu/environment/water/water-dangersub/pdf/commps_report.pdf.

http://ec.europa.eu/environment/water/water-dangersub/pdf/commps_report.pdf

http://ec.europa.eu/environment/water/water-dangersub/pdf/commps_report.pdf


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information on uses, restrictions and emissions of decaBDE has been reported in the present fact sheet. The EQS does not cover decaBDE. So far, there is not enough scientific background on these heterogeneous compounds as regards their effects assessment, even if historically, pentaBDE 99 came up as a representative of BDE toxicity. In general, mixture toxicity can only be predicted, if enough information is available on the single toxicity of the mixture components, which is not the case here as there is not enough data to derive an EQS for individual component of the commercial products. Furthermore, because of the high log KOW values there seems to be not even the possibility of using QSAR estimations for setting up a toxicity ranking between the mixture components. Integrative approach such as the Toxic Equivalent (TEQ) approach is not a way out since the representativeness of BDE congeners within the group is not scientifically defined yet at this stage. As long as it is deemed impossible to monitor every single of the 209 BDE congeners, an alternative is to work with a limited number of congeners which are usually monitored in the environment. The repartition pattern of the various congeners in the environment remains incompletely described. However, “Based on the analytical feasibility to measure the chemical compounds routinely in accredited laboratories, the production volumes [as registered in 2006], the occurrence of the chemical compounds in food and feed, their persistence in the environment and their toxicity” (EFSA, 2006), eight congeners were recommended by EFSA (EFSA, 2006): triBDE 28, tetraBDE 47, pentaBDE 99 and 100, hexaBDE 153 and 154, heptaBDE 183, and decaBDE 209. EFSA has further published a scientific opinion on PBDEs in food in 2011, analysing the information on these PBDEs in food samples provided by 11 Member states (EFSA, 2011) from 2001 to 2009. In this opinion, EFSA, 2011 underlines the analytical difficulties which remain for heptaBDE 183, and decaBDE 209.In line with EFSA recommendations, these indicators may be chosen as indicators congeners for BDE compounds in food, with the exception of decaBDE 209 which is not prioritised. With regards to heptaBDE183, in addition to analytical difficulties toxicological data are lacking for this compound. It is thus proposed to limit the list of indicators proposed by EFSA to six congeners: triBDE 28, tetraBDE 47, pentaBDE 99 and 100, hexaBDE 153 and 154. It is noted that:

- The data set available provides information on commercial mixture and individual compounds, and shows that PBDEs can cause a wide range of effects, in particular on mammals. The data set available however did not allow for the identification of one congener that would be systematically more toxic, or a mode of action that would be specific of one congener. Approaches such as toxic equivalent can not be applied. Therefore, for each protection goal, the use of the lowest available measured data in the overall dataset was adopted as worst case.

- Consequently, the compounds from which the QS were derived may not be the best marker of PAHs occurrence and effects on field;

- In line with the EFSA work, six indicators can be used as indicators congeners for BDE compounds, based on analytical feasibility, production volume and occurrence;

- It is recognised that the consideration of only 6 congeners for monitoring may be underprotective if an additive mode of action is assumed for all 209 BDE congeners,

- It is also recognised that it is deemed impossible to monitor every single of the 209 BDE congeners and the work made by EFSA in order to identify the most relevant marker, including consideration of occurrence, should be acknowledged.

Therefore, it is proposed to derive in this fact sheet a unique Environmental Quality Standard (EQS) for the pentaBDE and octaBDE, including data on their main components which are tetra-, penta-, hexa- and hepta-BDE where appropriate. This EQS value, expressed in µg.kg-1

food and proposed for compliance check with biota concentrations, will apply in monitoring terms to the sum of the following six indicator congeners in fish: triBDE 28, tetraBDE 47, pentaBDE 99 and 100, hexaBDE 153 and 154. During the review process, it was underlined that the current proposal might, in some cases, be less conservative than an approach where the sum of all BDEs would have been considered. It is noted that this would be the case in sampling sites where the six indicators are not the main contributors to the BDEs concentration.


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If Member States wished, after due justification, to apply EQS for sediment rather than biota, this could be done provided the same level of environment and human health protection is ensured. In this case, the EQS proposed in the present document should be back calculated to sediment ant could apply then to the same 6 congeners already recommended for biota2.

2 OctaBDE congeners 196 and 197 found in certain lakes (Unpublished data cordially forwarded by and belonging to Dr. Christoph Scheffknecht (Clara, pers. com. 2011)) were not recommended in addition of these 6 indicators above cited because according to SE’s opinion, more or less 50-100 congeners can possibly be analysed in non biological samples if the most sophisticated techniques available are used, but SE was of the opinion that even if 25 congeners or more could be analysed and quantified, it would just add uncertainty if all of these congeners were added to form the basis for an EQS. Therefore, other congeners such as BDE-196 and BDE-197 could be monitored but they would not be detected by most laboratories in a majority of samples. Finally, if these were found one would still not know how to interpret the result in terms of effects/risks.


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1 CHEMICAL IDENTITY

Common name Pentabromodiphenylether

Chemical name (IUPAC) Diphenyl ether, pentabromo derivative

Synonym(s)

Pentabrominated bi(di)phenyl ethers

Pentabrominated bi(di)phenyl oxides

Pentabrominated phenoxybenzene

Benzene, 1,1’ oxybis-, pentabromo derivative

PentaBDE

Chemical class (when available/relevant) Polybrominated diphenyl ethers

CAS number 32534-81-9

EC number 251-084-2

Molecular formula C12H5Br5O

Molecular structure

(example structure of a pentaBDE congener)

Molecular weight (g.mol-1) 564.7 3

Common name Octabromodiphenyl ethers

Chemical name (IUPAC) Diphenyl ether, octabromo derivative

Synonym(s)

Octabrominated bi(di)phenyl ethers

Octabrominated bi(di)phenyl oxides

Octabrominated phenoxybenzene

Benzene, 1,1’ oxybis-, octabromo derivative

OctaBDE

Chemical class (when available/relevant) Polybrominated diphenyl ethers

CAS number 32536-52-0

EU number 251-087-9

Molecular formula C12H2Br8O

Molecular structure

(example structure of an octaBDE congener)

3 Penta brominated compounds


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Molecular weight (g.mol-1) 801.384

4 Octa brominated compounds


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Nomenclature of all 209 BDE congeners.

Congener type No. Br sites





1 2 40 2,2’,3,3’ 82 2,2’,3,3’,4 129 2,2’,3,3’,4,5 170 2,2’,3,3’,4,4’,5 2 3 41 2,2’,3,4 83 2,2’,3,3’,5 130 2,2’,3,3’,4,5’ 171 2,2’,3,3’,4,4’,6

Mono- BDE

3 4 42 2,2’,3,4’ 84 2,2’,3,3’,6 131 2,2’,3,3’,4,6 172 2,2’,3,3’,4,5,5’ 4 2,2’ 43 2,2’,3,5 85 2,2’,3,4,4’ 132 2,2’,3,3’,4,6’ 173 2,2’,3,3’,4,5,6 5 2,3 44 2,2’,3,5’ 86 2,2’,3,4,5 133 2,2’,3,3’,5,5’ 174 2,2’,3,3’,4,5,6’ 6 2,3’ 45 2,2’,3,6 87 2,2’,3,4,5’ 134 2,2’,3,3’,5,6 175 2,2’,3,3’,4,5’,6 7 2,4 46 2,2’,3,6’ 88 2,2’,3,4,6 135 2,2’,3,3’,5,6’ 176 2,2’,3,3’,4,6,6’ 8 2,4’ 47 2,2’,4,4’ 89 2,2’,3,4,6’ 136 2,2’,3,3’,6,6’ 177 2,2’,3,3’,4,5’,6’ 9 2,5 48 2,2’,4,5 90 2,2’,3,4’,5 137 2,2’,3,4,4’,5 178 2,2’,3,3’,5,5’,6 10 2,6 49 2,2’,4,5’ 91 2,2’,3,4’,6 138 2,2’,3,4,4’,5’ 179 2,2’,3,3’,5,6,6’ 11 3,3’ 50 2,2’,4,6 92 2,2’,3,5,5’ 139 2,2’,3,4,4’,6 180 2,2’,3,4,4’,5,5’ 12 3,4 51 2,2’,4,6’ 93 2,2’,3,5,6 140 2,2’,3,4,4’,6’ 181 2,2’,3,4,4’,5,6 13 3,4’ 52 2,2’,5,5’ 94 2,2’,3,5,6’ 141 2,2’,3,4,5,5’ 182 2,2’,3,4,4’,5,6’ 14 3,5 53 2,2’,5,6’ 95 2,2’,3,5’,6 142 2,2’,3,4,5,6 183 2,2’,3,4,4’,5’,6

Di- BDE

15 4,4’ 54 2,2’,6,6’ 96 2,2’,3,6,6’ 143 2,2’,3,4,5,6’ 184 2,2’,3,4,4’,6,6’ 16 2,2’,3 55 2,3,3’,4 97 2,2’,3,4’,5’ 144 2,2’,3,4,5’,6 185 2,2’,3,3’,5,5’6 17 2,2’,4 56 2,3,3’,4’ 98 2,2’,3,4’,6’ 145 2,2’,3,4,6,6’ 186 2,2’,3,4,5,6,6’ 18 2,2’,5 57 2,3,3’,5 99 2,2’,4,4’,5 146 2,2’,3,4’,5,5’ 187 2,2’,3,4’,5,5’,6 19 2,2’,6 58 2,3,3’,5’ 100 2,2’,4,4’,6 147 2,2’,3,4’,5,6 188 2,2’,3,4’,5,6,6’ 20 2,3,3’ 59 2,3,3’,6 101 2,2’,4,5,5’ 148 2,2’,3,4’,5,6’ 189 2,3,3’,4,4’,5,5’ 21 2,3,4 60 2,3,4,4’ 102 2,2’,4,5,6’ 149 2,2’,3,4’,5’,6’ 190 2,3,3’,4,4’,5,6 22 2,3,4’ 61 2,3,4,5 103 2,2’,4,5’,6 150 2,2’,3,4’,6,6’ 191 2,3,3’,4,4’,5’,6 23 2,3,5 62 2,3,4,6 104 2,2’,4,6,6’ 151 2,2’,3,5,5’,6 192 2,3,3’,4,5,5’,6 24 2,3,6 63 2,3,4’,5 105 2,3,3’,4,4’ 152 2,2’,3,5,6,6’

Hepta- BDE

193 2,3,3’,4’,5,5’,6 25 2,3’,4 64 2,3,4’,6 106 2,3,3’,4,5 153 2,2’,4,4’,5,5’ 194 2,2’,3,3’,4,4’,5,5’ 26 2,3’,5 65 2,3,5,6 107 2,3,3’,4’,5 154 2,2’,4,4’,5,6’ 196 2,2’,3,3’,4,4’,5,6’ 27 2,3’,6 66 2,3’,4,4’ 108 2,3,3’,4,5’ 155 2,2’,4,4’,6,6’ 197 2,2’,3,3’,4,4’,6,6’ 28 2,4,4’ 67 2,3’,4,5 109 2,3,3’,4,6 156 2,3,3’,4,4’,5 198 2,2’,3,3’,4,5,5’,6 29 2,4,5 68 2,3’,4,5’ 110 2,3,3’,4’,6 157 2,3,3’,4,4’,5’ 199 2,2’,3,3’,4,5,5’,6’ 30 2,4,6 69 2,3’,4,6 111 2,3,3’,5,5’ 158 2,3,3’,4,4’,6 200 2,2’,3,3’,4,5,6,6’ 31 2,4’,5 70 2,3’,4’,5 112 2,3,3’,5,6 159 2,3,3’,4,5,5’ 201 2,2’,3,3’,4,5’,6,6’ 32 2,4’,6 71 2,3’,4’,6 113 2,3,3’,5’,6 160 2,3,3’,4,5,6 202 2,2’,3,3’,5,5’,6,6’ 33 2,3’,4’ 72 2,3’,5,5’ 114 2,3,4,4’,5 161 2,3,3’,4,5’,6 203 2,2’,3,4,4’,5,5’,6 34 2,3’,5’ 73 2,3’,5’,6 115 2,3,4,4’,6 162 2,3,3’,4’,5,5’ 204 2,2’,3,4,4’,5,6,6’ 35 3,3’,4 74 2,4,4’,5 116 2,3,4,5,6 163 2,3,3’,4’,5,6

Octa- BDE

205 2,3,3’,4,4’,5,5’,6 36 3,3’,5 75 2,4,4’,6 117 2,3,4’,5,6 164 2,3,3’,4,5’,6 206 2,2’,3,3’,4,4’,5,5’,6 37 3,4,4’ 76 2,3’,4’,5’ 118 2,3’,4,4’,5 165 2,3,3’,5,5’,6 207 2,2’,3,3’,4,4’,5,6,6’ 38 3,4,5 77 3,3’,4,4’ 119 2,3’,4,4’,6 166 2,3,4,4’,5,6

Nona- BDE

208 2,2’,3,3’,4,5,5’,6,6’

Tri- BDE

39 3,4’,5

78 3,3’,4,5

120 2,3’,4,4’,5

167 2,3’4,4’,5,5’ Deca-

BDE 209 2,2’,3,3’,4,4’,5,5’,6,6’ 79 3,3’,4,5’ 121 2,3’,4,5’,6 168 2,3’,4,4’,5’,6 80 3,3’,5,5’ 122 2,3,3’,4’,5’

Hexa- BDE

169 3,3’,4,4’,5,5’

Tetra- BDE

81 3,4,4’,5 123 2,3’,4,4’,5’ 124 2,3’,4’,5,5’ 125 2,3’,4’,5',6 126 3,3’,4,4’,5

Penta- BDE

127 3,3’,4,5,5’


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2 EXISTING EVALUATIONS AND REGULATORY INFORMATION

Legislation OctaBDE PentaBDE

Annex III EQS Dir. (2008/105/EC) Not Included Not Included

Existing Substances Reg. (793/93/EC)

Priority List No 1

EU-RAR finalised

(E.C., 2003)

Priority List No 2

EU-RAR finalised

(E.C., 2001)

Pesticides(91/414/EEC) No No

Biocides (98/8/EC) No No

PBT substances Not investigated under Dir. 67/548/EEC and Reg. 793/93/EC

Not investigated under Dir. 67/548/EEC and Reg. 793/93/EC

Substances of Very High Concern (1907/2006/EC) Not listed as such – October 2010 Not listed as such – October 2010

POPs (Stockholm convention) Not the octa derivative per se

Yes

Included in Annex A

Protocol of the 1979 Convention on LRATP5 on POPs Not the octa derivative per se Yes

Other relevant chemical regulation (veterinary products, medicament, ...)

Dir. 2002/95/EC and Reg. 552/2009/EC

Dir. 2002/95/EC and Reg. 552/2009/EC

Endocrine disrupter

Groshart and Okkerman, 2000

Petersen et al., 2007

Category 2 for human life for the 3 compounds, as well as the 2,2’,4,4’-tetraBDE.

Category 2 means “Potential for endocrine disruption. In vitro data indicating potential for endocrine disruption in intact organisms. Also includes effects in-vivo that may, or may not, be ED-mediated. May include structural analyses and metabolic considerations”

5 LRTAP: Long-Range Transboundary Air Pollution


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3 PROPOSED QUALITY STANDARDS (QS)

3.1 ENVIRONMENTAL QUALITY STANDARD (EQS)

QSbiota, hh for protection of human health from consumption of fishery products is 0.016 µg.kg-1biota ww and is

deemed the “critical QS” for derivation of an Environmental Quality Standard for the sum of polybrominated diphenyl ethers.

QSbiota, hh is based on mice dietary toxicity studies (Branchi et al., 2002; Branchi et al., 2005) consisting in exposure to BDE-99 during gestational and 21 post-natal days. A BMDL10 of 9 µg.kg-1

bw was derived, to which an internal daily dose of 4.2 ng.kg-1

bw.d-1 can be associated and an assessment factor of 30 is applied, given that toxico-dynamics differences between experimental animals and humans are already taken on board by the back calculation from BMDL10 to the daily dose. Therefore, the threshold level is deemed reliable.

Conversion from EQS in biota to an equivalent concentration into water should be considered with caution, since the BCF and BMF chosen for the conversion have been derived from data on individual compounds.

Value Comments

Proposed AA-EQS for [biota] [µg.kg-1biota ww]

Corresponding AA-EQS for [freshwater] [µg.l-1]

Corresponding AA-EQS in [marine water] [µg.l-1]

8.5 10-3

4.9 10-8

2.4 10-9

Critical QS is QSbiota, hh

See section 7

Proposed MAC-EQS for [freshwater] [µg.l-1]

Proposed MAC-EQS for [marine water] [µg.l-1]

0.14

0.014 See section 7.1

3.2 SPECIFIC QUALITY STANDARD (QS)

Protection objective6 Unit Value Comments

Pelagic community (freshwater) [µg.l-1] 0.049

Pelagic community (marine water) [µg.l-1] 0.0049 See section 7.1

[µg.kg-1 dw] 1 550 Benthic community (freshwater)

[µg.l-1] 2.1 10-5 – 0.433

[µg.kg-1 dw] 310 Benthic community (marine)

[µg.l-1] 4.1 10-6 – 8.6.10-2

See section 7.1

[µg.kg-1biota ww] 44

Predators (secondary poisoning) [µg.l-1]

2.5 10-4 (freshwater)

1.3 10-5 (marine waters)

See section 7.2

[µg.kg-1biota ww] 8.5.10-3 Human health via consumption of fishery

products [µg.l-1] 4.9 10-8 (freshwater)

See section 7.3

6 Please note that as recommended in the Technical Guidance for deriving EQS (E.C., 2011), “EQSs […] are not reported for ‘transitional and marine waters’, but either for freshwater or marine waters”. If justified by substance properties or data available, QS for the different protection objectives are given independently for transitional waters or coastal and territorial waters.


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2.4 10-9 (marine waters)

Human health via consumption of water [µg.l-1] 0.49.10-3


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4 MAJOR USES AND ENVIRONMENTAL EMISSIONS

4.1 RESTRICTIONS

PolyBDE, including pentaBDE and octaBDE, are mainly used as flame retardants. The use of pentaBDE and octaBDE is however restricted within the EU since August 15, 2004 (Commission regulation (EC) No 552/2009). PentaBDE and OctaBDE are not allowed to be placed on the market as substances, in mixtures or in articles in higher concentration than 0.1 % by weight.

Furthermore, use of polyBDEs in electrical and electronic products (E&Es) was restricted even earlier by the Directive 2002/95/EC (RoHS). From June 30, 2008, this directive covers also DecaBDE (Designation of the Chamber responsible for cases of the kind referred to in Article 104b of the Rules of Procedure of the Court of Justice 2008/C 116/02). This implies that the only permitted use of PBDEs in Europe is now the application of decaBDE in products other than E&Es. As a result of this new regulation, the majority of the previous use of decaBDE in the EU is now prohibited (corresponding to ca 80 percent of the total EU use in 2001). It is, however, still possible for industries to apply for exemptions for certain applications under the procedure laid out in article 5 of the RoHS Directive.

4.2 USES AND QUANTITIES

Stocks of products and articles flame retarded with polyBDE in higher concentrations than what is now permitted may however still exist in society due to their long service life. The products that are flame retarded with commercial polyBDE are often consumer available, such as TV-sets and computer housings, and thus common in homes and offices (La Guardia et al., 2006; WHO, 1994).

PolyBDE are flame retardants of the additive type, which means that they are physically combined with the material being treated rather than chemically combined (as in reactive flame retardants). Hence, there is the possibility that the flame retardant may diffuse out of the treated material to some extent (E.C., 2001; E.C., 2003).

OctaBDE was primarily used in acrylonitrile-butadiene-styrene (ABS) polymers (95 % of total EU use, at the time when the risk assessment report was written, E.C., 2003). In the final product, the content of octaBDE is 12-18 % by weight. Other uses are in high impact polystyrene (HIPS), polybutylene terephthalate (PBT), polyamide polymers, nylon, low density polyethylene polycarbonate, phenol-formaldehyde resins, unsaturated polyesters and in adhesives and coatings (E.C., 2003; OECD, 1994; WHO, 1994).

The major use of pentaBDPE was in flexible polyurethane foam for furniture and upholstery. Four main uses of polyurethane containing pentaBDPE have been identified in the EU. Around 95% was use in the manufacture of flexible polyurethane foams. These were used: a) in foam-based laminated automotive applications such as headrests; b) for domestic furniture, some of which includes cot mattresses ; and c) in foam-based packaging (E.C., 2001).

Information provided by industry indicates that there has been a decline in the import and hence usage of polyBDE in the EU in recent years.

PentaBDE is now included in Annex A (Elimination) to the Stockholm Convention and should not longer be on the EU market (UNEP, 2009b) as well as hexaBDE and heptaBDE contained in c-octaBDE (UNEP, 2009a).

4.3 ESTIMATED ENVIRONMENTAL EMISSIONS

Commercial pentaBDEs and octaBDEs are no longer produced within the EU (UNEP, 2006; UNEP, 2007), which means that there are no industrial point sources.


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Stocks of flame retarded products may however reside in society and as pentaBDE and octaBDE are physically combined with the material and not chemically bound there is a possibility of release from the material via diffusion. These emissions would thus occur mainly indoors and might enter the environment either via the ventilation streams or via the wastewater. Also after disposal there is a risk of environmental release of octaBDE from flame retarded products (E.C., 2001; E.C., 2003)

The estimated releases of penta- and octaBDE into the environment are summarised in the tables below.

Estimated releases of pentaBDE into the environment (E.C., 2001) Estimated releases (tonnes/year)

Source Receptor compartment Local scale (kg/d)

Regional scale a In the EU Continental

scale b To waste water 0.15 0.045 0.18 0.135 Polyurethane foam

manufacture To air 0.124 0.037 0.15 0.113 Polyurethane foam use To air - 4.3 43 38.7

To surface water - 0.53 5.26 4.73 To air - 0.002 0.021 0.019

Polyurethane foam “waste remaining in the environment” c To industrial soil - 1.59 15.86 14.27 Polyurethane foam disposal To landfill (or incineration) - 103.6 1.036 932.4

To waste water - 0.045 0.18 0.135 To surface water - 0.53 5.26 4.73 To air - 4.3 43.2 38.7 To industrial soil - 1.59 15.86 14.27

Total

To landfill (or incineration) - 103.6 1.036 932.4 a) The regional model is based on 10% of the total EU activity. However, for polyurethane foam manufacture the release at I single site accounts for more than 10% to the total release and so the region is assumed to contain this site as a worst case approach; b) Continental release = total EU release minus regional release; c) Release estimates for particulate matter containing pentaBDPE; d) In the EUSES modelling, a 70% connection rate to the waste water treatment plant is assumed.

Estimated releases of octaBDE into the environment (E.C., 2003) Estimated releases (tonnes/year)

Local scale* Regional scale* Continental scale* Use Receptor compartment 1994 1999 1994 1999 1994 1999

Polymers: handling of raw materials

To landfill / incineration (as dust) 0.08 0.024 0.54 0.095 4.86 0.85

To air 0.0191 0.0057 0.128 0.023 1.15 0.203 Polymers: compounding and conversion To waste water 0.0191 0.0057 0.128 a) 0.023 a) 1.15 a) 0.203 Polymers: service life To air as vapour - - 1.38 0.729 12.4 6.56

To industrial / urban soil - - 4.18 2.02 37.6 18.18 To air - - 0.006 0.0027 0.050 0.024

Polymers: “waste remaining in the environment” (service life and disposal) To surface water - - 1.39 0.669 12.5 6.02 Polymers: disposal To landfill / incineration - - 248 132 2 232 1 184

To air - - 1.51 0.755 13.60 6.79 To waste water via WWTP - - 0.090 0.016 0.805 0.142 Direct to surface water - - 1.43 0.676 12.85 6.08 To industrial / urban soil - - 4.18 2.02 37.6 18.18

Maximum total emission figure for regional and continental modelling

To landfill / incineration - - 249 132 2 237 1 185 * Local scale = at a site scale; Release in continental model = total release in EU – estimated release in regional model a) In the regional and continental model a 70% connection rate to the wastewater treatment plant is assumed. Therefore, 30% of these releases are taken as going direct to surface water.

Although estimated releases into the environment have substantially decreased between 1994 and 1999, it is worth noting that a Dutch study has demonstrated that the content of flame retardants in Dutch breast milk did not decline between 1998 and 2003, which is an evidence of the persistence and accumulation of this substance in the environment and which allow warning that decrease of releases does not necessarily means decrease of the concentrations in the environmental media (de Winter-Sorkina et al., 2006).


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5 ENVIRONMENTAL BEHAVIOUR

5.1 ENVIRONMENTAL DISTRIBUTION

Given that both c-pentaBDE and c-octaBDE are mixtures containing significant amounts of other brominated diphenyl ethers, notably tetra- and hexa- congeners for c-pentaBDE and hexa-, hepta- and nona- congeners for c-octaBDE, it was deemed of relevance to report hereunder physico-chemical parameters linked to environmental distribution for all the brominated diphenyl ethers above cited. In fact, these substances present physico-chemical similarities between each others that may allow a read-across of their ecotoxicological properties.

TetraBDE Master reference

Water solubility (mg.l-1) 0.011 (measured)

1.46 10-3 (estimated-EPI) E.C., 2003

Volatilisation TetraBDE is not likely to volatilize from water phase

Vapour pressure (Pa) 2.5 10-4 – 3.3 10-4 (measured)

3.2 10-5 (estimated-EPI) E.C., 2003

Henry's Law constant (Pa.m3.mol-1) 0.86 (estimated-EPI)

10.6 (estimated from vapour pressure and solubility) E.C., 2003

Adsorption TetraBDE is very likely to adsorb on particulate matter.

Organic carbon – water partition coefficient (KOC)

KOC= 565 860 (measured)

KOC= 71 560–122 900; 383 440 (estimated from KOW) E.C., 2003

Sediment – water partition coefficient (Ksed -water) 14 147 (calculated from KOC = 565 860) E.C., 2011

Hydrophobicity TetraBDE is a hydrophobic substance

Octanol-water partition coefficient (Log Kow)

5.87 – 6.16 (measured)

6.77 (estimated-EPI) E.C., 2003

Bioaccumulation – biomagnification cf. dedicated section 5.3


14

PentaBDE Master reference

Water solubility (mg.l-1)

13.3 10-3 (commercial, measured)

2.4 10-3 (measured for congener 2,2’,4,4’,5)

0.079 (estimated-EPI)

E.C., 2001

Volatilisation PentaBDE is not likely to volatilize from water phase

Vapour pressure (Pa)

4.69 10-5 (commercial, measured)

2.9 10-5 – 7.3 10-5 (measured)

3.3 10-6 (estimated-EPI)

E.C., 2001

Henry's Law constant (Pa.m3.mol-1)

0.36 (measured)

2 (commercial, estimated from vapour pressure and solubility)

0.78 – 522 (estimated from vapour pressure and solubility)

E.C., 2001

Adsorption PentaBDE is very likely to adsorb on particulate matter.


983 340 (measured)

215 080 – 556 801; 2 106 (estimated from KOW)

264 060 (commercial, estimated from KOW)

E.C., 2001

Sediment – water partition coefficient (Ksed -water) 5 378 – 13 921 (calculated from measured KOC) E.C., 2011

Hydrophobicity PentaBDE is a hydrophobic substance


6.57 (commercial, measured)

6.46 – 6.97 (measured)


E.C., 2001


HexaBDE Master reference

Water solubility (mg.l-1) 4.2 10-6 (estimated-EPI) E.C., 2003

Volatilisation HexaBDE is not likely to volatilize from water phase

Vapour pressure (Pa) 4.3 10-6 – 9.5 10-6 (measured)

3.8 10-7 (estimated-EPI) E.C., 2003


58.2; 659 – 1 456 (estimated from vapour pressure and water solubility)

E.C., 2003

Adsorption HexaBDE is very likely to adsorb on particulate matter

1 250 000 (measured)

453 520 – 3 270 000; 10 600 000 (estimated from KOW)

E.C., 2003

Organic carbon – water partition coefficient (KOC) measured estimated

2,2',4,4',5,5'-: 1 740 000 49 000 000

2,2',4,4',5,6'-: 2 690 000 40 700 000

Guan et al., 2009

Sediment – water partition coefficient (Ksed -water) 31 251 (calculated from measured KOC) E.C., 2011

Hydrophobicity HexaBDE is a hydrophobic substance


15


6.86 – 7.92 (measured)

8.55 (estimated-EPI) E.C., 2003



16

HeptaBDE Master reference


Volatilisation HeptaBDE is not likely to volatilize from water phase

Vapour pressure (Pa) 4.4 10-8 (estimated-EPI) E.C., 2003


144 (estimated from vapour pressure and solubility) E.C., 2003

Adsorption HeptaBDE is very likely to adsorb on particulate matter

55 800 000 (estimated from KOW) E.C., 2003 Organic carbon – water partition coefficient (KOC) measured estimated

2,2',3,4,4',5',6-: 1 480 000 115 000 000 Guan et al., 2009

Sediment – water partition coefficient (Ksed -water) 1 395 001 (calculated from estimated KOC) E.C., 2011

Hydrophobicity HeptaBDE is a very hydrophobic substance

Octanol-water partition coefficient (Log Kow) 9.44 (estimated-EPI) E.C., 2003


OctaBDE Master reference

Water solubility (mg.l-1) 5 10-4 (commercial, measured) 1.1 10-8 (estimated-EPI) E.C., 2003

Volatilisation OctaBDE is not likely to volatilize from water phase

Vapour pressure (Pa)

6.59 10-6 at 21°C (commercial, measured)

1.2 10-7 – 2.3 10-7 (measured)

4.9 10-9 (estimated-EPI)

E.C., 2003

Henry's Law constant (Pa.m3.mol-1)

0.03 (measured)

7.9 10-3 – 16 756 (estimated from vapour pressure and solubility)

10.6 (commercial, estimated from vapour pressure and solubility)

E.C., 2003

Adsorption OctaBDE is very likely to adsorb on particulate matter.


1 363 040 (extrapolated from measurements with other brominated diphenyl ethers)

7.3 106 – 2.93 108 (estimated from KOW)

156 640 (commercial, estimated from KOW)

E.C., 2003

Sediment – water partition coefficient (Ksed -water) 34 077 (calculated from extrapolated KOC) E.C., 2011

Hydrophobicity OctaBDE is a very hydrophobic substance


6.29 (commercial, measured)

8.35 – 8.9 (measured)


E.C., 2003



17

NonaBDE Master reference


Volatilisation NonaBDE is not likely to volatilize from water phase

Vapour pressure (Pa) 5.4 10-10 (estimated-EPI) E.C., 2003


849 (estimated from vapour pressure and solubility) E.C., 2003

Adsorption NonaBDE is very likely to adsorb on particulate matter

Organic carbon – water partition coefficient (KOC) 1.54 109 (estimated from KOW) E.C., 2003

Sediment – water partition coefficient (Ksed -water) 38 500 001 (calculated from estimated KOC) E.C., 2011

Hydrophobicity NonaBDE is a very hydrophobic substance

Octanol-water partition coefficient (Log Kow) 11.22 (estimated-EPI) E.C., 2003


5.2 ABIOTIC AND BIOTIC DEGRADATIONS

Master reference

Hydrolysis No information is currently available on the hydrolytic degradation of pentaBDE and octaBDE in aqueous solution. It is thought that these compounds will be hydrolytically stable under conditions found in the environment.

E.C., 2001

E.C., 2003

From the available information it is clear that polybrominated diphenyl ethers have the potential to photodegrade in the environment. In water, and at environmentally relevant wavelengths, the most likely initial reaction products from these reactions are hydroxylated diphenyl ethers, which possibly then react further. The first step in the reaction is probably cleavage of a C-Br following the absorption of radiation, followed by reaction of the radical intermediate (radical cation intermediates species may be formed in water) with oxygen and/or water to give substituted (e.g. hydroxylated) products (Larson and Weber, 1994; Mill and Mabey, 1985). The formation of lower brominated diphenyl ethers during direct photolysis in the environment would require the presence of H-atom donors at concentrations sufficiently high to compete with other oxidants for the aromatic radical intermediate formed. It is not possible to say anything about the significance or rates of these reactions for polybrominated diphenyl ethers in the environment.

E.C., 2001

E.C., 2003

DT50 – pentaBDE-99 ≈12,6 d (estimated from Syracuse Research Corporation AOP estimation program). E.C., 2001

In a mixture of methanol (80%) and water (20%) photolysis half-lives are:

DT50 – tetraBDE = 12 – 16 d DT50 – heptaBDE = 1.2 d

DT50 – pentaBDE = 2.4 d DT50 – octaBDE-203 = 5h

DT50 – hexaBDE = 1.2 d

Eriksson et al., 2001a quoted in E.C., 2003

Photolysis

HexaBDE-153 is rapidly photohydrodebrominated in aquatic systems to some of the most prevalent penta- and tetra-BDE typically observed in environmental matrices

Rayne et al., 2006

PentaBDE has been considered as Persistent in the framework of the POP Convention E.C., 2001 Biodegradation PentaBDE is not readily biodegradable according to a standard OECD test UNEP, 2006


18

with aerobic activated sludge. Biotic degradation of pentabromodiphenyl ether in sediment and water have not been reported in experimental studies but the half-lives for pentaBDE-99 and tetraBDE-47 have been estimated at 600 days (aerobic sediment) and 150 days (water) for both congeners.

In an experimental study, carps were fed with food spiked with individual BDE congeners for 62 days, and tissue and excreta were examined. Around 10% of pentaBDE-99 and 17% of heptaBDE-183 were reductively debrominated in the gut to lower brominated congeners, tetraBDE-47 and hexaBDE congeners, respectively, showing evidence of debromination into congener with one less bromine atom. Therefore, the authors showed that body burdens of BDE congeners in aquatic organisms may reflect direct uptake from exposure as well as debromination of more highly brominated congeners (Stapleton et al., 2004).

In another study (Munschy et al., 2011), accumulation and biotransformation of BDEs in fish (Solea solea) was observed. They showed that contamination efficiencies were related to their hydrophobicity potential and influenced biotransformation. Biotransformation was shown to be driven mostly by debromination process rather than biotransformation in hydroxylated metabolites.

Overall, several studies have been lead on diverse degradation processes which lead to debromination of BDE congeners. It is now considered that all highly brominated congener will end as low brominated congeners in environmental matrices (pers. comm., POP Review Committee, 2010).

5.3 BIOACCUMULATION AND BIOMAGNIFICATION POTENTIAL

Congeners BCF fish Master reference

tetraBDE 28 800 – 35 100 (measured)

19 480 – 37 090; 46 050 (estimated from log KOW) E.C., 2003

pentaBDE

44 550 (commercial, estimated from log KOW)

1 440; 17 700 (measured)

34 141; 43 061 – 45 880 (estimated from log KOW)

E.C., 2001

5 640 (measured)

46 180 – 27 260; 12 200 (estimated from log KOW) E.C., 2003

hexaBDE

up to 2 580 and 5 640 depending on the congener CITI, 1982 quoted in UNEP, 2007

heptaBDE 2 100 (estimated from log KOW) E.C., 2003

39 980 (commercial, estimated from log KOW)

6 670 – 16 390; 175 (estimated from log KOW) E.C., 2003

octaBDE

Experimental results indicate that octaBDE does not bioconcentrate. A single study on a mixed commercial octabromodiphenyl ether product indicated essentially no bioaccumulation in carp (Cyprinus carpio) (CBC, 1982 cited in E.C., 2003). Assuming that the actual concentration of octabromodiphenyl ether in the water was around 0.5 µg/l, BCFs would be of the order of <10-36 l/kg. Bioconcentration is however considered relevant for hexaBDE, which is included in the commercial octaBDE product (see BCF values for hexaBDE congeners in the corresponding table above.

E.C., 2003

nonaBDE 7 (estimated from log KOW) E.C., 2003

Congeners BAF Master reference

triBDE

Freshwater food web (South-China reservoir surrounded by several e-waste recycling workshops) including invertebrates (1 snail and 1 prawn species), fish (3 carp species) and snakes (2 species): BDE-28: BAFsnail = 794

Wu et al., 2008


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Lake trouts from Lake Michigan7

BDE-47: BAFtrout = 19.9 106 Streets et al., 2006

tetraBDE No available information

pentaBDE

Lake trouts from Lake Michigan7

BDE-99: BAFtrout = 5 106

BDE-100: BAFtrout = 31.6 106

Streets et al., 2006

hexaBDE See details above for TriBDE-28. BDE-154: BAFsnail = 199 526 Wu et al., 2008

7 In their study, Streets et al. (2006) report very high values of BAF compared to the other study reported above (Wu et al., 2008). This may be partly explained by the large differences in exposure scenarios. In fact, water concentrations reported in Streets et al. (2006) are ca. 1 000 times lower compared to water concentrations reported by Wu et al. (2008) or 3 times lower to Law et al. (2006), while concentrations in lake trout in Lake Michigan (Streets et al., 2006) are higher compared to data fish concentrations from Lake Geneva (Cheaib et al., 2009, cf. section 6.2). Furthermore, Lake trout has very high lipid content (approx. 15%) and is a high trophic level species which could also partly explain the high values of BAF.


20

Congeners Biomagnification parameters Master reference TMF values

Marine food web including invertebrates (5 species), fish (9 species) and seabirds (2 species): BDE-28: TMF = 1.47 (invertebrates and fish) BDE-28: TMF = 3.2 (seabirds)

Zhang et al., 2010

triBDE Freshwater food web (reservoir surrounded by several e-waste recycling workshops) including invertebrates (1 snail and 1 prawn species), fish (3 carp species) and snakes (2 species): BDE-28: TMF = 1.64

Wu et al., 2009

BDE-47: TMF = 1.6 (significantly ≠ from 1) BDE-49: TMF = 1.2 BDE-66: TMF = 0.44 (significantly ≠ from 1)

Kelly et al., 2008

Marine food web including invertebrates (5 species), fish (9 species) and seabirds (2 species): BDE-47: TMF = 3.91 (invertebrates and fish) BDE-47: TMF = 19.54 (seabirds)

Zhang et al., 2010

Freshwater food web (reservoir surrounded by several e-waste recycling workshops) including invertebrates (1 snail and 1 prawn species), fish (3 carp species) and snakes (2 species): BDE-47: TMF = 2.28

Wu et al., 2009

tetraBDE

Freshwater food web including phytoplankton, zooplankton, mussels and fish (6 species): BDE-47: TMF = 1.5

Law et al., 2006

Trophic magnification factors not significantly different from 1 in an Arctic marine food web BDE-99: TMF = 0.76 BDE-100: TMF = 0.96

Kelly et al., 2008

Marine food web including invertebrates (5 species), fish (9 species) and seabirds (2 species):

BDE-99: TMF = 3.21 (invertebrates and fish) BDE-99: TMF = 84.72 (seabirds)


Zhang et al., 2010

Freshwater food web (reservoir surrounded by several e-waste recycling workshops) including invertebrates (1 snail and 1 prawn species), fish (3 carp species) and snakes (2 species): BDE-99: TMF = 0.53 BDE-100: TMF = 2.64

Wu et al., 2009

pentaBDE

Freshwater food web including phytoplankton, zooplankton, mussels and fish (6 species): BDE-99: TMF = 0.7 BDE-100: TMF = 1.6

Law et al., 2006

Trophic magnification factors not significantly different from 1 in an Arctic marine food web BDE-153: TMF = 0.59 BDE-154: TMF = 0.46

Kelly et al., 2008

Marine food web including invertebrates (5 species), fish (9 species) and seabirds (2 species):



Zhang et al., 2010 hexaBDE

Freshwater food web (reservoir surrounded by several e-waste recycling workshops) including invertebrates (1 snail and 1 prawn species), fish (3 carp species) and snakes (2 species):

Wu et al., 2009


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Congeners Biomagnification parameters Master reference TMF values

BDE-153: TMF = 0.81 BDE-154: TMF = 2.25 Marine food web including invertebrates (5 species), fish (9 species) and seabirds (2 species): BDE-183: TMF = 0.53 (invertebrates and fish) BDE-183: TMF = 13.68 (seabirds)

Zhang et al., 2010

heptaBDE Freshwater food web (reservoir surrounded by several e-waste recycling workshops) including invertebrates (1 snail and 1 prawn species), fish (3 carp species) and snakes (2 species): BDE-183: TMF = 0.81

Wu et al., 2009

octaBDE No data available nonaBDE No data available

Marine food web including invertebrates (5 species), fish (9 species) and seabirds (2 species): SumBDEs: TMF = 2.37 (invertebrates and fish) SumBDEs: TMF = 29.17 (seabirds)

Zhang et al., 2010

SumBDEs Freshwater food web (reservoir surrounded by several e-waste recycling workshops) including invertebrates (1 snail and 1 prawn species), fish (3 carp species) and snakes (2 species): SumBDEs: TMF = 1.86

Wu et al., 2009

Congeners Biomagnification parameters (continued) Master reference

Single BMF1 values BMFzoopk – fish = 1.48 (liver) ; 2.25 (muscle) BMFfish.pred – fish.prey = 1.12 – 1.59 (livre) ; 1.07 – 1.17 (muscle)

Kuo et al., 2010 tetraBDE BDE-47 Range (geometric mean):

BMFzoopk – zoopk = 10.9 (4.1 - 29.1) BMFzoopk – fish = 2.6 (0.4 - 10.1)

Sørmo et al., 2006

BAFfish = 16 – 20 (Bioaccumulation factors, defined as concentration in fish / concentration in food)

Holm et al., 1993 as cited in E.C., 2001

BDE-99: BMFzoopk – fish = 0.4 (liver) ; 0.73 (muscle) BDE-99: BMFfish – fish = 0.88 – 0.89 (liver) ; 0.49 – 0.61 (muscle) BDE-100: BMFzoopk – fish = 1.45 (liver) ; 1.52 (muscle) BDE-100: BMFfish – fish = 1.14 – 1.41 (liver) ; 1.09 – 1.18 (muscle)

Kuo et al., 2010

pentaBDE

Range (geometric mean): BDE-99: BMFzoopk – zoopk = 5.6 (0.65 - 47.6) BDE-99: BMFzoopk – fish = 0.9 (0.04 - 3.4) BDE-100: BMFzoopk – fish =0.6 (0.2 ; 1.6)

Sørmo et al., 2006

hexaBDE Biomagnification factors estimated for two hexaBDE isomers for several food chains examples, using the North Sea data: BMFfish – invertebrate = ~0.6 – 0.7

de Boer et al., 2001 as cited in E.C., 2003

heptaBDE No data available octaBDE No data available nonaBDE No data available


22

Congeners Biomagnification parameters (continued) Master reference Single BMF2 values

BMFpolar bear – ringed seal : geometric mean of 5 locations (range) BDE-47: 3.5 (1.8 – 7.4)

Muir et al., 2006

BMFharbor seal – fishes : range (geometric mean of 7 marine fish species) BDE-47: 38.1 (21.4 – 109) BDE-49: 0.4 (0.12 – 1.03) BDE-66: 0.1 (0.04 – 0.83) BDE-75: 0.3 (0.05 – 0.63)

Shaw et al., 2009

BDE-47: BMFmammal - fish 56 BDE-47: BMFmammal - mammal 0,5

Sørmo et al., 2006

tetraBDE

Mean +/- s.d.: BDE-47: BMFharbor seal – fish = 8.4 +/- 5.7 (juveniles) ; 4.6 +-/ 2.4 (adults) BDE-47: BMFharbor porpoise – fish = 18 +/- 21(juveniles) ; 15 +/- 10 (adults)

Weijs et al., 2009

Geometric mean of 5 locations (range) BDE-99: BMFpolar bear – ringed seal = 4.5 (1 – 11) BDE-100: BMFpolar bear – ringed seal = 3.1 (0.6 – 8.8)

Muir et al., 2006

Range (geometric mean of 7 marine fish species) BDE-99: BMFharbor seal – fishes = 37.6 (17.9 – 213) BDE-100: BMFharbor seal – fishes = 10.3 (6.9 – 29.8)

Shaw et al., 2009

BDE-99: BMFringed seal – fish = 13.7 BDE-99: BMFpolar bear – ringed seal = 0.3 BDE-100: BMFringed seal – fish = 26.1 BDE-100: BMFpolar bear – ringed seal = 0.3

Sørmo et al., 2006 pentaBDE

Mean +/- s.d.: BDE-99: BMFharbor seal – fish = 5.9 +/- 6.1 (juveniles) ; 2.9 +/- 1.2 (adults) BDE-99: BMFharbor porpoise – fish = 19 +/- 24 (juveniles) ; 33 +/- 23 (adults) BDE-100: BMFharbor seal – fish = 1.7 +/-1.1 (juveniles) ; 1.3 +/- 0.7 (adults) BDE-100: BMFharbor porpoise – fish = 13 +/- 15 (juveniles) ; 15 +/- 9.7 (adults)

Weijs et al., 2009

Biomagnification factors estimated for two hexaBDE isomers for several food chains examples, using the North Sea data: BMFporpoise – fish = 40 – 70 BMFseal – fish = 5 – 10

de Boer et al., 2001 as cited in E.C., 2003

BMFpolar bear – ringed seal : geometric mean of 4 locations (range) BDE-153: BMF= 49.6 (8.8 – 130) BDE-154: BMF= 1.0 (0.2 – 2.9)

Muir et al., 2006

BMFharbor seal – fishes : range (geometric mean of 7 marine fish species) BDE-153: 367.7 (148 – 700) BDE-154: 26.4 (11.3 – 447) BDE-155: 64.0 (12.4 – 236)

Shaw et al., 2009

BDE-153: BMFpolar bear – ringed seal = 7.5 BDE-154: BMFringed seal – fish = 7.9 BDE-154: BMFpolar bear – ringed seal = 0.32

Sørmo et al., 2006

hexaBDE

Mean +/- s.d.: BDE-99: BMFharbor seal – fish = 15 +/- 13 (juveniles) ; 15 +/- 7.8 (adults) BDE-99: BMFharbor porpoise – fish = 17 +/- 21 (juveniles) ; 77 +/- 53 (adults) BDE-100: BMFharbor seal – fish = 2.2 +/-1.5 (juveniles) ; 4.8 +/- 3.6 (adults) BDE-100: BMFharbor porpoise – fish = 16 +/- 17 (juveniles) ; 50 +/- 32 (adults)

Weijs et al., 2009

heptaBDE No data available octaBDE No data available nonaBDE No data available


23

BMF value derived from Osprey egg based on measurements in egg, several fish species and their relative contribution in Osprey diet: BMFfish – birds eggs = 25.1

Chen et al., 2010 SumBDEs

BMFharbor seal – fishes = 17.1 – 76.5 Shaw et al., 2009

Overall, measured BCF values for BDE congeners range from very low values for highly brominated congeners (<5) to very high values for lower brominated congeners (up to 35 100 (measured value) for tetraBDE). Considering the fact that any highly brominated BDE congeners ends as debrominated via diverse degradation processes, the highest measured BCF of 35 100 for tetraBDE congeners should be retained. This choice is consistent with the application of the worst case.

Looking at the values reported here above, the single BMF1 values are in a range below 10 for all BDE congeners. However, looking more closely at these values, it appears that maximal BMF1 values (5.6 and 10.9) are encountered only for a specific trophic interval, i.e. from zooplankton to zooplankton. The third maximal value is reported by Sormo et al. (2006) 2.6 for BMF1 from zooplankton to fish.

Thus, a value of 5 for BMF1 could be proposed, that covers almost all trophic chains among the ones reported in TMF studies, except the ones including top predators, e.g. seabirds. In line with the TGD-EQS, the food chain is defined with its trophic levels as water –BCF→ aquatic organisms –BMF1→ fish → fish-eating predator for freshwater ecosystems. It seems therefore that a BMF1 value of 5 would be appropriate to cover biomagnification from lower trophic levels to fish species. Such a value is still a worst case, considering the high BAF values reported by Streets and his collaborators (2006) as well as the wide range of BMF values in general. For marine ecosystems, however, another trophic level may be introduced: water –BCF→ aquatic organisms –BMF1→ fish –BMF2→ fish-eating predator → top predator. As regards BMF2, the values reported above are rather low for tetraBDE congeners other than BDE-47, but some very high values are reported for tetraBDE-47 as well as some values for pentaBDE, the highest values being reported for hexaBDE congeners. Indeed, values as high as 700 are reported by Shaw et al. (2009) for hexaBDE-153. However, on the overall, it is more frequent to encounter values between 10 and 70.TMF studies show a high degree of biomagnification for top predators, e.g. seabirds. The data reported by Kelly et al., 2008 however indicate a low degree or absence of biomagnification of PBDEs in a marine Arctic food web. The authors explain that the field observations suggest PBDEs exhibit a relatively rapid rate of depuration though biotransformation in Arctic marine organisms, which is consistent with laboratory studies in fish and rats. Considering the high variability of the data reported and additional evidence that BDEs can be eliminated by top predators, a BMF2 value of 20 is proposed as reasonable worst case.


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6 AQUATIC ENVIRONMENTAL CONCENTRATIONS

6.1 ESTIMATED CONCENTRATIONS

Production of c-pentaBDE and c-octaBDE no longer occurs in the EU. Therefore, the following figures extracted from EU-RARs are reported hereunder for information only. Information is also available on hexaBDE component, a main constituent of both c-pentaBDE and c-octaBDE.

Predicted environmental concentration (PEC)

Compartment c-octaBDE

(1999 – 1994)

HexaBDE

component c-pentaBDE

PEClocal – production

Emission period

Annual average

7 – 41.7

1.6 – 11.4

-

0.37

0.305

PEClocal – polymer processing

Emission period

Annual average

0.27

0.025 – 0.08

0.017 – 0.019

-

PECregional (dissolved) 3.6 10-3 – 7.5 10-3 1.5 10-4 – 1.6 10-3 1.5 10-3

Freshwater

(µg.l-1)

PECcontinental (dissolved) 5.6 10-4 – 1.2 10-3 - 6 10-4

Wastewater treatment plant (µg.l-1)

PEClocal – polymer processing 8 - -

Marine waters (µg.l-1) No information available

PEClocal –production 20 700 – 1 236 000 - 4 490

PEClocal – polymer processing 8 000 400 – 430 -

PECregional 190 – 390 6.2 – 63 32

Freshwater sediment

(µg.kg-1 ww) PECcontinental 29 – 60 - 0.013

Marine sediment (µg.kg-1 ww) No information available

PECfish – polymer processing 0.057 – 0.18 8.6 – 13 - Biota (freshwater) (µg.kg-1 ww) PECearthworms – polymer processing 5 340 – 5 570 670 – 690 -

Biota (marine) No information available

Biota (marine predators) No information available


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6.2 MEASURED CONCENTRATIONS

Compartment Site Component Measured environmental

concentration (MEC)8 Master reference

TetraBDE 47 PEC1= - ; PEC2= 0.01; Max= -

Anal*: 0 / 606

PentaBDE 99 PEC1= 0.0025; PEC2= 0.1; Max= 0.003

Anal*: 5 / 1 459

PentaBDE 100 PEC1= - ; PEC2= 0.1; Max= -

Anal*: 0 / 910

HexaBDE 153 PEC1= - ; PEC2= 0.05; Max= -

Anal*: 0 / 1 049


Anal*: 0 / 659

Freshwater and marine waters (µg.l-1) EU

OctaBDE PEC1= 0.05 ; PEC2= 0.25; Max= 0.25

Anal*: 1 / 9 827

James et al., 2009

and

EU monitoring database9

TetraBDE 47 Range = 46 10-6 – 205 10-6

PentaBDE 99 Range = 46 10-6 – 181 10-6

PentaBDE 100 Range = 13 10-6 – 29 10-6

HexaBDE 153 Range = 14 10-6 – 38 10-6

HexaBDE 154 Range = 9 10-6 – 25 10-6

Freshwater (µg.l-1) FR - River Seine (total water)

HeptaBDE 183 Range = 10 10-6 – 32 10-6

Labadie et al., 2010

Marine waters (µg.l-1) No data available

WWTP effluent (µg.l-1) No data available

8 Anal : nb quantified analysis / nb all analysis 9 http://www.priority.substances.wfd.oieau.fr/indexRank.php

http://www.priority.substances.wfd.oieau.fr/indexRank.php

http://www.priority.substances.wfd.oieau.fr/indexRank.php


26


concentration (MEC) Master reference

Sed < 2 mm OctaBDE PEC1= 1.2 ; PEC2= 50; Max= 38.5

Anal*: 278 / 1 775

TetraBDE 47 PEC1= 6.85 ; PEC2= 6.85; Max= 7.7

Anal*: 18 / 22

PentaBDE 99 PEC1= 9.1 ; PEC2= 9.1; Max= 10.5

Anal*: 10 / 17

PentaBDE 100 PEC1= 1 ; PEC2= 0.8; Max= 1

Anal*: 1 / 25

HexaBDE 153 PEC1= 1 ; PEC2= 1 ; Max= 1.1

Anal*: 2 / 24

Sed 20 µm


Anal*: 0 / 16

Sed 63µm

EU

No data available

James et al., 2009

and


TriBDE 28 Range = 5.7 10-4 – 0.034

TetraBDE 47 Range = 0.018 – 0.66

PentaBDE 99 Range = 0.016 – 1.3

PentaBDE 100 Range = 3.5 10-3 – 0.025

HexaBDE 153 Range = 3.2 10-3 – 0.16

HexaBDE 154 Range = 2.2 10-3 – 0.18

IT - Lake Maggiore

HeptaBDE 183 Range = 6.8 10-3 – 0.18

Mariani et al., 2008

TriBDE28 0.031

TetraBDE 47 0.74

PentaBDE 99 0.51

PentaBDE 100 0.098

HexaBDE 153 0.056

HexaBDE 154 0.064

HeptaBDE 183 0.079

OctaBDE 196/200 0.022

OctaBDE 197/204 0.033

Sediment (µg.kg-1

dw)

Sediment fraction not reported

CH – Greifensee

(2001)

Σ octaBDE 194, 196, 197, 198, 201, 202 and 205 0.14 + increasing trend

Kohler et al., 2008


27






HexaBDE 153 Range = 0.77 – 1.15

HexaBDE 154 Range = > LOD – 0.98

ES – rivers Anoia and Cardener

HeptaBDE 183 Range = < LOD – 1.23

Labandeira et al., 2007



PentaBDE 100 Range = 0.092 – 0.54

HexaBDE 153 Range = 0.07 – 0.13

HexaBDE 154 Range = 0.05 – 0.1

FR – River Seine (total water)

HeptaBDE 183 Range = 0.02 – 0.09

Labadie et al., 2010

TriBDE28 Median (range) = 1.4 (nd – 2.1)

TetraBDE 47 Median (range) = 11 (2 – 49)

PentaBDE 99 Median (range) = 4.8 (1.3 – 34)

PentaBDE 100 Median (range) = 1.5 (0.5 – 10)

HexaBDE 153 Median (range) = 3.8 (2.6 – 8.1)

HexaBDE 154 Median (range) = nd (nd – 1.8)

HeptaBDE 183 Median (range) = 16 (4.5 – 24)

OctaBDE 196 Median (range) = 16 (11 – 20)

AT – remote lakes

OctaBDE 197 Median (range) = 14 (7.1 – 20)

TriBDE28 Median (range) = 240 (57 – 1200)

TetraBDE 47 Median (range) = 340 (30 – 1100)

PentaBDE 99 Median (range) = 66 (17 – 360)

PentaBDE 100 Median (range) = 21 (4.5 – 110)

HexaBDE 153 Median (range) = 7 (3.7 – 38)

HexaBDE 154 Median (range) = 1.3 (0.62 – 27)

HeptaBDE 183 Median (range) = nd (nd – 38)

OctaBDE 196 Median (range) = 61 (5.5 – 210)

AT – lakes influenced by anthropogenic uses

OctaBDE 197 Median (range) = 44 (10 – 350)

Unpublished data cordially forwarded by and belonging to Dr. Christoph Scheffknecht (Clara, pers. com. 2011)

HexaBDE 153 0.01 (mean)

HexaBDE 154 0.02

HeptaBDE 183 Not detected

Sediment (µg.kg-1

dw)

(continued)

Sediment fraction not reported

(continued)

Canada – Hudson Bay and Hudson Strait

(1999-2003)

HeptaBDE 183 < 0.1

Kelly et al., 2008


28



TetraBDE 47 PEC1= 7 ; PEC2= 4.5; Max= 36.7

Anal*: 97 / 127

PentaBDE 99 PEC1= 0.115 ; PEC2= 0.088 ; Max= 0.123

Anal*: 38 / 103

PentaBDE 100 PEC1= 10 ; PEC2= 2.5; Max= 15

Anal*: 22 / 127

HexaBDE 153 PEC1= 11.7 ; PEC2= 2.5; Max= 15

Anal*: 8 / 127

Biota fresh and marine water (µg.kg-

1ww)

Invertebrates EU

HexaBDE 154 PEC1= 11.7 ; PEC2= 2.5; Max= 15

Anal*: 7 / 127

James et al., 2009

and


TriBDE 28 <LOD – 4.7

TetraBDE 47 23.1 – 309.5

PentaBDE 99 5.0 – 69.5

PentaBDE 100 2.3 – 29.5

HexaBDE 153 <LOD – 7.0

HexaBDE 154 <LOD – 6.6

Zebra mussel IT – Lake Maggiore

HeptaBDE 183 <LOD – 6.3

Binelli et al., 2008

HexaBDE 153 Range = <0.86 – 24

HexaBDE 154 Range = <0.86 – 27 Fish – diverse species10

-> as lipid weight

IT – Po River

HexaBDE 155 Range = <0.86 – 7

Viganò et al., 2008

TetraBDE 47 Range = 18.5 – 565

PentaBDE 99 Range = < LOD – 7.04

PentaBDE 100 Range = < LOD – 82.2

HexaBDE 153 Range = < LOD – 26.7

HexaBDE 154 Range = < LOD – 84.3

Fish – feral carp

-> as lipid weight

ES - Rivers Anoia and Cardener

HeptaBDE 183 Range = < LOD – 25.5

Labandeira et al., 2007

TriBDE 28 Median (range) = 3.6 (1.3 – 6.6)

TetraBDE 47 Median (range) =104 (48 – 189)

PentaBDE 99 Median (range) = 46 (24 – 127)

PentaBDE 100 Median (range) =14 (5.2 – 31)



Fish – Lake trout

-> as lipid weight CH – Lake Geneva

HeptaBDE 183 Median < LOD (LOD = 0.14)

Cheaib et al., 2009

Σ HexaBDE 153 + HexaBDE 154 < 0.1 – 5.7 Fish – Eel

-> as lipid weight HeptaBDE 183 < 0.1 – 0.2

Σ HexaBDE 153 +

HexaBDE 154 < 0.1 – 0.1

Biota freshwater (µg.kg-1

ww)

Fish – Pike-perch

-> as lipid weight

NL – freshwaters

HeptaBDE 183 < 0.1

van Leeuwen and de Boer, 2008

10 bleak, nase, gudgeon, chub and barbel


29



HexaBDE 153 0.021 – 0.26

HexaBDE 154 0.18 – 3.4

HexaBDE 155 0.13 – 0.4

HeptaBDE 183 <0.001 – 0.035

Fish (n=8)

Roach muscle

OctaBDE 203 <0.002

HexaBDE 153 <0.006 – 8.7

HexaBDE 154 0.094 – 11

HexaBDE 155 <0.006 – 2.4

HeptaBDE 183 <0.001 – 0.069

Fish (n=33)

Perch muscle

-> as lipid weight

OctaBDE 203 <0.002 – 0.30

HexaBDE 153 0.60 – 36

HexaBDE 154 2.0 – 52

HexaBDE 155 0.51 – 10

HeptaBDE 183 <0.001 – 6.0

Fish (n=25)

Pike muscle

-> as lipid weight

Baltic Sea – Åland archipelago

OctaBDE 203 <0.002 – 1.8

Burreau et al., 2004

Fish – Herring

-> as lipid weight Mean (Range) = 22.2 (18.5 – 26)

Fish – Sprat

-> as lipid weight Mean (Range) = 10.5 (8.7 – 12.3)

Fish – Salmon

-> as lipid weight

Baltic Sea TetraBDE 47

Mean (Range) = 25.1 (16.7 – 33.6)

Szlinder-Richert et al., 2010

TriBDE 28 Mean (Range) = 0.05 (<LOQ – 0.06)

TetraBDE 47 Mean (Range) = 0.59 (0.39 – 0.83)

PentaBDE 99 Mean (Range) = 0.22 (<LOQ – 0.51)


HexaBDE 153 Mean (Range) = non detected

HexaBDE 154 Mean (Range) = non detected

Biota marine (µg.kg-1

ww)

Fish – Herring and sprat

-> as wet weight

Greater North Sea

HeptaBDE 183 Mean (Range) = non detected

Carlsson et al., 2011

TetraBDE 47 Range = 15 – 3 800

PentaBDE 99 Range = 110 – 9 200

PentaBDE 100 Range = 77 – 5 200

HexaBDE 153 Range = 270 – 16 000

HexaBDE 154 Range = 50 – 4 400

HeptaBDE 183 Range = 43 – 1 300

HeptaBDE 184 Range = <1.3 – 54

HeptaBDE 185 Range = <3.6 – 42

OctaBDE 196 Range = 9.1 – 190

OctaBDE 197 Range = 18 – 220

Birds – Peregrine falcon eggs

-> as lipid weight

SE (N and SW)

OctaBDE 203 Range = <2.1 – 180

Johansson et al., 2009

TriBDE 28 Mean (Range) = non detected

TetraBDE 47 Mean (Range) =0.28 (0.15 – 0.55)


Biota marine predators (µg.kg-1

ww)

Birds – Common eider eggs

-> as wet weight

Greater North Sea

PentaBDE 100 Mean (Range) = non detected



30



HexaBDE 153 Mean (Range) < LOQ

HexaBDE 154 Mean (Range) = 0.22 (< LOQ – 0.29)

HeptaBDE 183 Mean (Range) = non detected

TriBDE 28 Mean (Range) < LOQ


PentaBDE 99 Mean (Range) = 1.39 (0.33 – 3.21)


HexaBDE 153 Mean (Range) = 0.61 (>LOQ – 1.19)

HexaBDE 154 Mean (Range) =0.36 (>LOQ – 0.73)

Birds – Herring gull eggs

-> as wet weight

Greater North Sea

HeptaBDE 183 Mean (Range) = 0.58 (>LOQ – 0.09)


TriBDE 28 Mean (Range) < LOQ






Birds – Herring gull liver

-> as wet weight

Greater North Sea

HeptaBDE 183 Mean (Range) = unknown (>LOQ –)


TriBDE 28 Mean (Range) = 0.032 (0.014 – 0.074)

TetraBDE 47 Mean (Range) = 4.4 (0.62 – 26)

PentaBDE 99 Mean (Range) =0.57 (0.21 – 1.4)


HexaBDE 153 Mean (Range) = 0.4 (0.076 – 1.8)

HexaBDE 154 Mean (Range) = 0.48 (0.052 – 3.1)

Mammals – Ringed seal (liver)

-> as wet weight

Baltic Sea

HeptaBDE 183 Mean (Range) = 0.013 (0.003 – 0.075)

Routti et al., 2009

HexaBDE 153 <0.09 – 6 090

HexaBDE 154 <0.2 – 613

HexaBDE 155 <0.1 – 805

HeptaBDE 183 <1.7 – 45

Mammals – Harbour seal (blubber)

-> as lipid weight

USA – NW Atlantic (Long

Island and Gulf of Maine)

OctaBDE 197 <0.02 – 57

Shaw et al., 2008

HexaBDE 153 0.13 – 2.9

HexaBDE 154 0.02 – 53

Mammals – Beluga (blubber, n: 35)

-> as lipid weight HeptaBDE 183 0.02 – 0.27

HexaBDE 153 0.03 – 5.5

HexaBDE 154 0.02 – 1.18

Mammals – Ringed seal (blubber, n: 11)

-> as lipid weight

Canada – Hudson Bay and Hudson

Strait (1999-2003)

HeptaBDE 183 50 and 40 (female and male)

Kelly et al., 2008


31

7 EFFECTS AND QUALITY STANDARDS

The data reported in this section hereafter correspond to the most relevant effect data extracted from pentaBDE and octaBDE EU-RAR (E.C., 2001; E.C., 2003).

7.1 ACUTE AND CHRONIC AQUATIC ECOTOXICITY

The data considered as valid for effects assessment purpose in the RAR were not further assessed. Concentrations are all expressed as in commercial products when commercial products were tested. Since EU-RARs were published in 2001, 2002 and 2003, other studies were available on exposure of aquatic organisms to PBDE congeners and/or commercial products. Some are reported in the table hereunder and were assessed for their reliability, but there are numerous articles (e.g. Crump et al., 2008; Muirhead et al., 2005; Raldúa et al., 2008; Timme-Laragy et al., 2006) which report endpoints that are not usually accepted as effects assessment endpoints (developmental and behavioural effects, genotoxic effects, dietary exposure instead of direct exposure). Other studies have not been validated because not deemed reliable enough for effects assessment purpose (e.g. Breitholtz and Wollenberger, 2003; Key et al., 2008). Only studies which could be attributed a Klimisch code (Klimisch et al., 1997) 1 or 2 were reported in the tables.


32

7.1.1 Organisms living in the water column ACUTE EFFECTS Reliability Master reference

No information available

Freshwater Selenastrum capricornutum / 96h Compound tested: c-pentaBDE 24h-EC10 = 2.7 10-3 – 3.1 10-3 48h and 96h : no effects observed

Evaluated in EU-RAR (E.C., 2001)

Palmer et al., 1997c Algae & aquatic plants (mg.l-1)

Marine

Skeletonema costatum / 72h / growth rate

Compound tested: TetraBDE (BDE-47)

48h-EC50= 0.07

48h-NOEC= 6.6 10-3

2 Källqvist et al., 2006

No information available Daphnia magna / 48 h Compound tested: c-pentaBDE EC50 – mortality, immo = 0.014 (mm) NOECmortality, immo = 4.9 10-3 (mm)

Palmer et al., 1997a

Freshwater Daphnia magna / 21d Compound tested: c-pentaBDE 96h-EC50immo =0.017 (mm) 7-21d-EC50immo = 0.014 (mm)


Drottar and Krueger, 1998

Marine No information available

Invertebrates (mg.l-1)

Sediment No information available Oryzias latipes / 48h Compound tested: c-pentaBDE, c-octaBDE and c-decaBDE 48h-LC50 > 500 for the three compounds

Evaluated in EU-RARs

(E.C., 2001; E.C., 2002; E.C., 2003)

CITI, 1982

Freshwater Oncorhynchus mykiss / 96h Compound tested: c-pentaBDE 96h-LC50 and NOEC > 0.021


Palmer et al., 1997b


Fish (mg.l-1)

Sediment No information available mm : mean measured concentrations

Notes regarding some of the acute tests reported in the table above: Selenastrum capricornutum / 96h / c-pentaBDE (Palmer et al., 1997c as cited in E.C., 2001)

The effects observed after 24h of exposure had disappeared by 48 hours exposure. The results of this study, and significance of the effects seen, are difficult to interpret, as it appears that the test substance was removed from solution (by adsorption onto the algal cells) during the experiment, but it may indicate that the commercial pentaBDE has the potential to cause effects on algae at similar concentrations as seen in long-term studies with Daphnia magna.

Skeletonema costatum / 96h / tetraBDE (Källqvist et al., 2006)

Because of the high specific growth rate (2.35/d) in the control, the exponential phase was not maintained for 72 h in the control and at the two lowest concentrations of BDE 47, and analysis of the data therefore was based on growth rates measured during the first 48 h. Although lead over a 72h-exposure duration, this study can not be used to provide chronic data as such.

Daphnia magna / 48 h / c-pentaBDE (Palmer et al., 1997a as cited in E.C., 2001)

It was stated in the test report that the effects seen could have been due to physical impairment (undissolved test substance adsorbed onto the daphnids and adversely affecting respiration, swimming, etc.) rather than a direct toxic effect.


33

Oryzias latipes (CITI, 1982 and Palmer et al., 1997b as cited in E.C., 2001)

No effects were observed up to the highest concentration tested, which were far above the water solubility of the compound tested.

CHRONIC EFFECTS Valid according to Master reference

Freshwater

Selenastrum capricornutum / 96h

Compound tested: c-pentaBDE

24h-EC10 = 2.7 10-3 – 3.1 10-3

48h and 96h : no effects observed

Evaluated

in EU-RAR

(E.C., 2001)

Palmer et al., 1997c Algae & aquatic plants

(mg.l-1) Marine No information available

Daphnia magna / 21d


21d-NOECgrowth = 5.3 10-3 (mm)

Evaluated

in EU-RAR

(E.C., 2001)

Drottar and Krueger, 1998

Daphnia magna / 21d

Compound tested: c-octaBDE

NOECsurvival, repro, growth > 0.002 (n)

NOECsurvival, repro, growth > 1.7 10-3 (m)

Evaluated in

EU-RAR

(E.C., 2003)

Graves et al., 1997 Freshwater

Daphnia magna / 21d / reproduction

Compound tested: TetraBDE (BDE-47)

NOEC= 0.014

2 Källqvist et al., 2006

Invertebrates

(mg.l-1)


Freshwater

Oncorhynchus mykiss / ELS / 87 days


60d post-hatch-NOECgrowth = 8.9 10-3 (mm)

Evaluated

in EU-RAR

(E.C., 2001)

Wildlife, 2000d

Marine

Psetta maxima / ELS (part)

- 2d exposure of embryos

NOECtetraBDE-47= 2.03 10-3

NOECpentaBDE-99= 3.22 10-3

- 4d exposure of larvae

NOECtetraBDE-47= 4.9 10-4

NOECpentaBDE-99= 1.61 10-3

2 Mhadhbi et al., 2010

Fish

(mg.l-1)

Sediment No information available

Other taxonomic groups No information available

om: organic matter content; oc: organic carbon content; n: nominal concentrations; mm: mean measured concentrations Notes regarding some of the chronic tests reported in the table above:

Selenastrum capricornutum / 96h / c-pentaBDE (Palmer et al., 1997c as cited in E.C., 2001)

See acute toxicity section.


34

Daphnia magna / 21d / c-octaBDE (Graves et al., 1997 as cited in E.C., 2003)

Since octaBDE is a mixture of congeners between hexa- to nonaBDE, some consideration has to be given as to whether the lower brominated components, particularly the hexaBDE, could be more toxic than indicated by the results of the test. In the test, stock solutions of the test substance were prepared by dissolving in dimethylformamide, with one stock solution being prepared for each concentration tested. These stock solutions were then injected into the diluter mixing chambers to give the desired test concentrations, with the solvent concentration being 0.07 ml/l in all cases. This method ensures that the composition of the substance in solution is as close as possible to that in the commercial preparation, providing all the test substance enters into solution. Since the hexaBDE component is likely to be the most soluble of all the components in the commercial octaBDE, it is very likely that this component was present in true solution and so the concentration of this component can be estimated from the nominal concentration using the known composition of the commercial substance tested (e.g. 5.5% hexaBDE). Thus the NOEC of >2 µg/l for the commercial compound is equivalent to a NOEC of >0.11 µg/l for the hexaBDE component.

In section 5.1, the water solubility of the hexaBDE component is estimated/extrapolated to be around 47 µg/l. Thus it is theoretically possible for the hexaBDE isomers to be present in solution at concentrations higher than those used in this experiment. As part of the 21-day reproduction test carried out for the commercial octaBDE, a range finding 9-day Daphnia immobilisation test was carried out using higher nominal concentrations (0.0081, 0.027, 0.09, 0.3 and 1 mg/l) of the commercial octaBDE. Details of the test system used are not reported. Deaths occurred in seven out of the ten exposed Daphnia at the 1 mg/l nominal concentration after two to three days but no other mortalities were noted. The numbers of neonates produced were reported as 32 in the control, 21 in the solvent control, 0 at 0.0081 mg/l, 19 at 0.027 mg/l, 27 at 0.09 mg/l 0 at 0.3 mg/l and 0 at 1.0 mg/l. The significance of these results is unknown. The test concentrations used in this range finding test exceed the water solubility of the substance by a considerable amount and thus the mortality seen at 1 mg/l could have been due to a physical effect caused by undissolved test substance. However, it is possible that the effects seen were related to the dissolved chemical. Since the nominal concentration tested was well in excess of the water solubility of the commercial mixture, then each component of the mixture could be present in solution at concentrations close to their individual solubilities. If this is assumed then the effects seen could be due to the most water soluble component of the commercial mixture at a concentration of around 4.7 µg/l. The results of this analysis should be treated with caution due to the assumptions made, and the fact that the experiment was a range finding, rather than definitive, test.

Daphnia magna / 21d / tetraBDE (Källqvist et al., 2006)

The distribution of the individual data shows a larger variation at 14 mg.l-1 than in the control. Three animals at this exposure level had a higher number of offspring than the average for the control animals, whereas the remaining seven animals showed lower reproductive output than the control mean. Although the high variation in reproduction at 14 mg.l-1 may, in itself, be an effect of exposure to BDE 47, further studies to reveal the toxicological relevance were not undertaken.

Psetta maxima / ELS / tetraBDE and pentaBDE (Mhadhbi et al., 2010)

Missing information on material and methods, notably on water quality parameters such as dissolved oxygen and pH.

QSwater, eco derivation

Chemicals considered: The ecotoxicological data retrieved on aquatic organisms address ecotoxicity of the commercial mixture c-pentaBDE as well as c-octaBDE as well as some data on individual tetra- and penta-congeners, BDE 47 and BDE 99, respectively. The best satisfactory approaches would be either:

- to derive congener-specific QS values which would allow EQS compliance with concentrations of these congeners in the media, or

- to identify the most toxic congener and use it as a reference in a toxic equivalence approach for the determination of an overall EQS.

Most of the tests were conducted on commercial mixture and it is not possible to derive congener-specific QS values based on the commercial product ecotoxicological data because even if the content of the different congeners in each commercial product is well-known, the contribution of these congeners to the overall toxicity is not well-attested.

There are not enough reliable congener-specific ecotoxicological data available to allow the derivation of congener-specific QS values or identify the most toxic congener. Moreover, there were not enough congener-specific data to range the BDE congeners as a function of their toxicity. It is rather well-known that according to their physico-chemical properties, the more brominated the less soluble and the less bioaccumulative (for higher bromination levels) the congeners are, but it is not possible to presume on their direct toxicity properties based on this information.


35

Based on the information available, and considering the relationships between BDE congeners (i.e., possibilities for higher brominated compounds to degrade in lower brominated compounds) it is proposed to use all the data from the cited commercial products and their main components. The dataset contain data for algae, invertebrates and fish for acute and chronic exposures, and QS values will be derived based on the worst case basis, i.e. derived from the lowest acute and chronic ecotoxicological data.

Freshwater versus marine waters data: The Guidance Document on EQS derivation (E.C., 2011) states that “in principle, ecotoxicity data for freshwater and saltwater organisms should be pooled for organic compounds, if certain criteria are met” and that “the presumption that for organic compounds saltwater and freshwater data may be pooled must be tested, except where a lack of data makes a statistical analysis unworkable.”

This is the case for polybrominated diphenyl ethers. In fact, there are too few marine data (solely one acute data on marine algae and one marine data on marine flatfish) to perform a “meaningful statistical comparison” and no further indications of “a difference in sensitivity between freshwater vs saltwater organisms”. Therefore, in this case, the data sets may be combined for QS derivation according to the Guidance Document on EQS derivation (E.C., 2011).

QS derivation: As explained above, the acute and chronic dataset can be considered as complete (data available for algae, invertebrates and fish) and the lowest available data are used to derive QS useful for the sum of BDEs, thus to be compared to the sum of the available BDEs monitored in the media. The lowest available data are found for exposure of Daphnia magna for acute exposures, with a 48h-EC50 of 14 µg.l-1 and for turbot Psetta maxima embryos exposed 4d, with a NOEC of 0.49 tetraBDE µg.l-1. These toxicity data are equal or below water solubility of the different BDE component tested, i.e. 13 µg.l-1 for c-pentaBDE and 11 µg.l-1 for tetraBDE. QS can therefore be derived on the basis of the lowest available ecotoxicological data. Algae, crustaceans and fish being represented for both acute and chronic dataset, standard assessment factors of 100 and 1000 can be applied to the lowest data to derive MACfreshwater, eco and MACmarine water, eco, respectively. Standard assessment factors of 10 and 100 are applied to the lowest data to derive AA-QSfreshwater, eco and AA-QSmarine water, eco, respectively. Tentative QSwater

Assessment factor method Relevant study for derivation of QS AF Tentative QS

MACfreshwater, eco 100 0.14

MACmarine water, eco

Daphnia magna / 48 h EC50 – mortality, immo= 0.014 mgc-pentaBDE.l-1 1000 0.014

AA-QSfreshwater, eco 10 0.049

AA-QSmarine water, eco

Psetta maxima / 4d exposure of larvae

NOEC= 4.9 10-4 mgtetraBDE.l-1 100 0.0049

7.1.2 Sediment-dwelling organisms

SEDIMENT – CHRONIC EFFECTS Valid according to Master reference

Spiked sediment test / 28d


Hyalella azteca

<2% om-28d-NOECsurvival, growth = 6.3 (n) Wildlife, 2000a

Sediment

dwelling

invertebrates

(mg.kg-1dw)

Chironomus riparius

<2% om-28d-NOECsurvival, growth = 16 (m)

Evaluated

in EU-RAR

(E.C., 2001)

Wildlife, 2000b


36

Lumbriculus variegatus

<2% om-28d-NOECsurvival, repro, growth > 3.1 (n) Wildlife, 2000c

Lumbriculus variegatus / 28d / Spiked sed

Compound tested: c-octaBDE

• c-octaBDE:

2.4% oc-NOECsurvival, repro, growth >1 340 (mm)

5.9% oc-NOECsurvival, repro, growth >1 272 (mm)

Evaluated

in EU-RARs (E.C., 2003)

Krueger et al., 2001a; Krueger et al., 2001b

Commercial pentaBDE exposure 28d spiked sediment tests

According to the Guidance Document on EQS derivation (E.C., 2011), for sediment organisms, the NOEc should be normalised to the standard organic matter or organic carbon content of sediment. The actual organic carbon contents of the sediments used in the tests are unknown and organic matter content are reported as <2% in each test. Since organic matter contents are usually very approximately two times higher than the organic carbon contents, this would imply that the organic carbon contents of the sediments used were very low at <1%. Assuming this value, the NOEC values of 6.3, 16 and 3.1 mg.kg-1

dw, are equivalent to lowest NOEc of 30.5, 48 and 15.5 mg.kg-1dw.

Lumbriculus variegatus / 28d (Krueger et al., 2001a; Krueger et al., 2001b as cited in E.C., 2003)

The amount of hexaBDE component present in the commercial octaBDE tested was not given. If it is assumed that the test substance contained 5.5% hexaDE (typical of current products) then the estimated NOECs for the hexaBDE component alone based on these results would be ≥74 mg/kg dry weight for the 2.4% organic carbon content sediment and ≥70 mg/kg dry weight for the 5.9% organic carbon content sediment.

QSsediment derivation A QSsediment can be estimated from the use of sediment-dwelling organisms toxicity data by applying an assessment factor of 10 to the lowest NOEC from the 5%oc long-term studies of 15.5 mg.kg-1

dw. The TGD-EQS recommends favouring the use of chronic tests carried out on benthic organisms when available for the derivation of QSsediment. Only results obtained with commercial mixtures c-penta-BDE and c-octa-BDE are available for benthic organisms, and they may be considered as acceptable since PBDEs occurs in mixture in the environment. For pelagic species however, the QS is based on a result obtained with tetra-BDE which lead to the lowest NOEC. For comparison purpose then, QSsediment is then also calculated using the equilibrium partitioning method from the test conducted on Psetta maxima with tetra-BDE. The comparison shows that the experimental result is comprised within the range of calculated values using the equilibrium partitioning method, although the large range of Koc available for PBDE must be emphasised. Whatever the compound used for the derivation of QSsediment, and the method applied, the results are higher than the overall EQS driven by the human health protection. In line with the EQS-TGD, the lowest endpoint from experimental data on benthic organisms is preferred. Tentative QSwater

Assessment factor method Relevant study for derivation of QS AF Tentative QS

Lumbriculus variegatus / 28d / 5% oc

NOEC > 15.5 mg.kg-1dw

NOEC > 5.96 mg.kg-1ww

10

596 µg.kg-1ww

1 550 µg.kg-1dw

corresponding(2) to

2.1 10-5 – 0.433 µg.l-1 AA-QSfreshwater, sed.


NOEC= 4.9 10-4 mgtetraBDE.l-1

EqP Additional

AF of 10(1)

0.049 µg.l-1

corresponding(2) to

6.7 – 1.4.105 µg.kg-1ww

17.5 – 3.7.105 µg.kg-1dw


37

Lumbriculus variegatus / 28d / 5% oc

NOEC > 15.5 mg.kg-1dw

NOEC > 5.96 mg.kg-1ww

50

119 µg.kg-1ww

310 µg.kg-1dw

corresponding(2) to

4.1 10-6 – 8.6.10-2 µg.l-1 AA-QSmarine water, sed.


NOEC= 4.9 10-4 mgtetraBDE.l-1

EqP Additional

AF of 10(1)

0.0049 µg.l-1

corresponding(2) to

0.7 – 1.4.104 µg.kg-1ww

1.75 – 3.7.104 µg.kg-1dw

(1) an additional assessment factor of 10 is being applied given the high KOW values of BDE congeners and commercial products (log KOW > 5) to take into account the possible ingestion of sediment. (2) corresponding values in water using conversion via Equilibrium Partitioning (EqP) method with KOC-BDE congeners= 71 560 – 1.5 109 l.kg-1

.


38

7.2 SECONDARY POISONING

According to the Guidance Document on EQS derivation (E.C., 2011), c-pentaBDE and c-octaBDE as well as all their main components (tetra- to nona-congeners) trigger the bioaccumulation criteria given the high values of log KOW (above 5), the high values of BCF (mostly above 1 000) and that the toxicity data reported for oral toxicity of mammals which demonstrate a somewhat high toxicity (NOEC as low as 0.4 mg.kg-1

feed ww, see below).

Oral exposure is expected to be the most relevant exposure pathway for BDEs. Biota-sediment accumulation factors for hexaBDE and heptaBDE on two freshwater fish species were reported between 1 and 3 and it was concluded that 100% of the exposure was associated to food or food plus sediment (van Beusekom et al., 2006).

As for direct toxicity (see section 7.1), the interpretation of the toxicity data for BDE compounds is not straight forward as data are not available for all congeners separately and as the relative toxicity of these congeners is not elucidated.

The available physico-chemical properties and BCF values (see section 5.1) indicate that tetraBDE as well as pentaBDE and hexaBDE congeners have a much higher bioconcentration potential than the other components of pentaBDE and octaBDE commercial products (heptaBDE, octaBDE and nonaBDE congeners) and so are likely to have a higher potential to cause adverse effects on organisms in the environment. Wherever possible, the effects of the tetraBDE, pentaBDE and hexaBDE components are considered in interpreting the toxicity data for deriving secondary poisoning linked QS.

The data considered as valid for effects assessment purpose in the RAR were not further assessed. Since EU-RARs were published in 2001, 2002 and 2003, other studies were available on dietary exposure of birds and mammals to PBDE congeners and/or commercial products. Some are reported in the table hereunder and were assessed for their reliability, but there are numerous articles which report endpoints that are not usually accepted as effects assessment endpoints such as developmental and behavioural effects and/or single dose dietary exposure (Viberg et al., 2003a; Kuriyama et al., 2005; Viberg et al., 2006), exposure through egg cell (McKernan et al., 2009).

In an in vitro study (Frouin et al., 2010), it was shown that immune system of marine mammals was affected when harbour seal cells were exposed to 5.8 mg BDE-47.l-1, 6.8 mg BDE-99.l-1 and 7.7 mg BDE-153.l-1, respectively. However, these data are not dietary exposure data and therefore not usable for calculating QSbiota, sec.pois. value.

Secondary poisoning of top predators Master reference

Rats / Oral / 30 d / effects on liver / exposure to c-pentaBDE

NOAEL = 0.45 mg.kg-1.d-1 E.C., 2001 Mammalian oral toxicity

CD-1 Swiss mice / oral administration (by trained self-administration from a modified syringe once a day or via gavage to dams) of 0.6, 6, 18 or 30 mg BDE-99.kg-1

bw from GD6 to PND21

Effects: hyperactivity and alterations in anxiety-like behavior

LOAEL = 0.6 mg.kg-1bw.d-1

NOAEL= 0.2 mg.kg-1bw.d-1 (CFLOAEL->NOAEL=3)

NOEC= 4 mg.kg-1food (CFNOAEL->NOEC=20)

Branchi et al., 2002



39

Male mice / oral administration of one single dose of 0.8 and 12 mg BDE-99.kg-1

bw

Effects: neurotoxicity


Eriksson et al., 2001b

Sprague-Dawley rats / administration by gavage to a dose of 2 mg.kg-1

bw.d-1 from GD6 to PND21

Effects: poor short-term memory when tested in the Morris water maze at PND34-36, and lower antioxidant enzyme activity in the brain at PND37

Cheng et al., 2009

Wistar rats / administration by gavage of a single dose of 0.06 and 0.3 mg pentaBDE-99 (98% purity).kg-1

bw / rats dosed at GD 6

Effects : reduced sperm production in male offspring at adulthood (age: 150 d) and effects on motor activity

As the exposure was a single exposure of the dams, the offspring were exposed in utero but also post-natally through lactation. Therefore, it was not possible to calculate the actual internal dose that the offsprings were exposed to in this study. It is however likely that the body burden in the offspring during the period studied would be lower but not far lower than the body burden of the dams. LOAEL= 0.06 mg.kg-1

bw.d-1

Kuriyama et al., 2005

Rat / Oral / 13 weeks / Increased liver weight

Dietary exposure to c-octaBDE

LOAEL= 7.2 mg.kg-1bw.d-1

NOAEL= 2.4 mg.kg-1bw.d-1 (CFLOAEL->NOAEL=3)

NOEC= 48 mg.kg-1biota ww (CFNOAEL->NOEC=20)

Great Lakes Chemical Corporation, 1977

as cited in E.C., 2003

Rabbit / Oral /exposure days 7-19 of gestation / foetotoxicity

Dietary exposure to c-octaBDE

NOAEL= 2 mg.kg-1bw.d-1

NOEC= 66.6 mg.kg-1biota ww (CFNOAEL->NOEC =33.3)

Breslin et al., 1989 as cited in E.C., 2003

Negative correlation between concentration ΣpolyBDE in egg and average productivity for Falco peregrinus.

Congeners 2,2',4,4',5,5'-HexaBDE ; 2,2',4,4',5,6'-HexaBDE and 2,2',3,4,4',5',6-HeptaBDE constituting approx 50% of total PBDE.

Johansson et al., 2009

Avian oral toxicity

Falco sparverius / oral / 71d year-1 / Increased time to egg laying, decreased thickness and mass of eggshell, decreased hatching and reproductive success.

Dietary exposure to c-pentaBDE (0.3 and 1.6 mg.kg-1.d-1)

Resulting concentrations in eggs: ca. 290 and 1 100 mg.kg-1ww.

Time to egg laying, thickness and mass of eggshell significantly associated with concentrations of 2,2',4,4',5,5'-HexaBDE (73 mg.kg-1

ww, mean) and 2,2',4,4',5,6'-HexaBDE (48 mg.kg-1ww,

mean) in eggs.

Fernie et al., 2009

As for aquatic ecotoxicity, results are available mainly for the commercial mixtures of c-pentaBDE and c-octaBDE. The information on individual congener is insufficient to determine the contribution of each compound to the overall toxicity of the mixtures. The lowest LOAEL= 0.06 mg.kg-1

bw.d-1 is from the study from Kuriyama et al., 2005 where pentaBDE-99 (98% purity) was administered to rats. According to the Joint FAO/WHO expert committee on food additives (JECFA, 2006b; JECFA, 2006a), some “dioxin-like” effects found with BDE compounds are supposed to be mainly due to minor “dioxin-like”, non-BDE contaminants (i.e. impurities of the commercial mixtures). Moreover, Bakker and its collaborators (Bakker et al., 2008) state that “PBDE impaired postnatal


40

spermatogenesis resulting from prenatal exposure has been reported as the most sensitive toxic effect of PBDE toxicity with a LOAEL in rats of 60 µg.kg-1

bw (Kuriyama et al., 2005). However, for the same effect a NOAEL of 12.5 ng.kg-1

bw was reported for 2,3,7,8-TCDD (Ohsako et al., 2001). Thus, a BDE 99 solution of more than 99.99% purity is needed to exclude 2,3,7,8-TCDD as cause for the observed toxicity. This is significantly higher than the reported 98% purity of the solution actually used (Kuriyama et al., 2005). As none of the BDE solutions used in toxicity studies fulfills the mentioned purity criterion, the outcome of these studies is ambiguous”. In summary, there is thus an obvious kinetic similarity between BDEs and dioxins whereas the mechanistic similarities are much weaker. Therefore, the use of the lowest Ah-receptor-dependent endpoints (such as reduced sperm production in male offspring at adulthood by Kuriyama et al.) may not be relevant until this ambiguity has been solved. Studies with purified BDE material has however confirmed that effects on liver, thyroid and developmental and neurotoxic effects can also be attributed to BDEs. The next lowest NOEC= 0.4 mg.kg-1

food is derived from a test in which pregnant rats administered a single dosage of c-pentaBDE exhibited reduced sperm production in male offspring at adulthood.

Given the data set available and the above considerations, it is proposed to use the studies of Branchi et al. (2002, 2005) for the determination of the QSbiota, sec. pois.

Overall, BCF values for BDE congeners range from very low values for highly brominated congeners to very high values for lower brominated congeners. Considering the fact that any highly brominated BDE congeners ends as debrominated via diverse degradation processes, the highest measured BCF of 35 100 for tetraBDE congeners should be retained. This choice is consistent with the application of the worst case (see section 5.1).

Moreover, values chosen to be applied as BMF1 and BMF2 values are 5 and 20, respectively (see section 5.1).

Therefore, for the derivation of BDEs QSbiota secpois, the following bioaccumulation and biomagnification values are used: BCF=35 100, BMF1 = 5 and BMF2 = 20.

Tentative QSbiota sec. pois. Relevant study for derivation of QS Assessment

factor Tentative QS

Biota NOEC= 4 mg.kg-1food 90 (1)

44.4 µg.kg-1biota ww

corresponding to

2.5 10-4 µg.l-1 (freshwater)

1.3 10-5 µg.l-1 (marine waters)

(1) An assessment factor of 90 is deemed appropriate to take account of extrapolation of QS from NOEC given that the corresponding study consists in exposure of sensible life stages during gestational and post natal periods.

Given the above considerations on bioaccumulation and biomagnification issues (see section 5.3 and above in section 7.2), the fact that these properties depend on the congener considered, and given that biota repartition depends largely on geographical parameters, the recommendation of a given biota to monitor is more particularly tricky. However, it is well acknowledged that most BDEs covered in the present fact sheet do bioconcentrate (e.g. tetraBDE, pentaBDE and hexaBDEs) and that some BDEs do biomagnify along the trophic food chain. Therefore, fish should be recommended as the trophic level to monitor when considering BDE congeners (ideally it would even be recommendation of a carnivorous fish).


41

7.3 HUMAN HEALTH

According to the Guidance Document on EQS derivation (E.C., 2011), pentaBDE and octaBDE compounds trigger the bioaccumulation criteria given the high values of log KOW (above 6), the high values of BCF (above 1 000) and that the toxicity data reported for oral toxicity of mammals which demonstrate a somewhat high toxicity (NOEC as low as 0.4 mg.kg-1

feed ww, see below).

Human health via consumption of fishery products Master reference

Rats / Oral / 30 d / effects on liver / exposure to c-pentaBDE

NOAEL = 0.45 mg.kg-1.d-1 E.C., 2001

CD-1 Swiss mice / oral administration (by trained self-administration from a modified syringe once a day or via gavage to dams) of 0.6, 6, 18 or 30 mg BDE-99.kg-1

bw from GD6 to PND21

Effects: hyperactivity and alterations in anxiety-like behavior




Male mice / oral administration of one single dose of 0.8 and 12 mg BDE-99.kg-1

bw

Effects: neurotoxicity


Eriksson et al., 2001b

Sprague-Dawley rats / administration by gavage to a dose of 2 mg.kg-1

bw.d-1 from GD6 to PND21

Effects: poor short-term memory when tested in the Morris water maze at PND34-36, and lower antioxidant enzyme activity in the brain at PND37

Cheng et al., 2009

Wistar rats / administration by gavage of a single dose of 0.06 and 0.3 mg pentaBDE-99 (98% purity(1)).kg-1

bw / rats dosed at GD 6

Effects: reduced sperm production in male offspring at adulthood (age: 150 d) and effects on motor activity

As the exposure was a single exposure of the dams, the offspring were exposed in utero but also post-natally through lactation. Therefore, it was not possible to calculate the actual internal dose that the offsprings were exposed to in this study. It is however likely that the body burden in the offspring during the period studied would be lower but not far lower than the body burden of the dams.


Kuriyama et al., 2005

Mammalian oral toxicity

Rabbit / Oral /exposure days 7-19 of gestation / fetotoxicity / exposure to c-octaBDE

NOEC= 66.6 mg.kg-1biota ww

Breslin et al., 1989

as cited in E.C., 2003

CMR

Not classified as carcinogenic or mutagenic

OctaBDE Classified as reprotoxic 1B = Presumed human reproductive toxicant, i.e. there is evidence from animal studies of adverse effect on sexual function and fertility, or on development in the absence of other toxic effects, or if occurring together with other toxic effects the adverse effect on reproduction is considered not to be a secondary non-specific consequence of other toxic effects.

E.C., 2008

(1) Because BDE-99 was not tested at 99.9% purity, potential dioxin-like effects can not be excluded.


42

The Joint FAO/WHO expert committee on food additives conducted a Safety evaluation of certain contaminants in food (JECFA, 2006b; JECFA, 2006a) in which they identified a number of difficulties, in particular the complexity of a group of related chemical for which data on individual congeners are lacking. As regards their toxicity potential, BDE compounds have shown various responses, such as Ah-receptor-dependent responses, e.g. thyroid hormone perturbation (Hallgren and Darnerud, 2002; Zhou et al., 2002; Stoker et al., 2004), hepatic CYP 1A1 enzyme induction (Peters et al., 2004), impaired spermatogenesis (Kuriyama et al., 2005)), neurodevelopmental toxicity (Eriksson et al., 2001b; Eriksson et al., 2002; Viberg et al., 2003b; Viberg et al., 2003c; Viberg et al., 2004; Viberg et al., 2006; Sand et al., 2004), or neurobehavioural toxicity (Branchi et al., 2002). For the same reasons as stated in the section dealing with secondary poisoning of top predators, the study of Kuriyama et al. (2005) may not be relevant until the ambiguity about Ah-receptor dependent endpoints has been solved.

A BMDL10 value for pentaBDE-mediated hepatic CYP2B induction in male rats is reported to be 0.07 mg.kg-

1bw.d-1 and no clear evidence for marked differences in CYP-inducing potency of tetraBDE or pentaBDE can

be derived from the available literature. Moreover, changes in hepatic drug metabolism and transthyretin expression seem to play a key role in the decrease in serum T4 observed in rodents and BDEs can generate a decrease in apolar hepatic retinoids with a BMDL10 value in male rats estimated to 0.5 mg.kg-1

bw.d-1.

Following a body-burden approach, a BMDL10 for BDE-99 of 9 µg.kg-1bw is recommended, to which an

internal daily dose of 4.2 ng.kg-1bw.d-1 can be associated taking account of a longest human half-life

for BDE-99 of 1 442 days.

Given the above considerations on the weakness of the argumentation in favour of taking account of Ah-receptor-dependent endpoints, the former threshold level (based on LOAEL from Branchi’s studies) should be used for the derivation of the QSbiota, hh.

As for secondary poisoning section, for the derivation of BDEs QSbiota hh, the following bioaccumulation and biomagnification values are used: BCF=35 100, BMF1 = 5 and BMF2 = 20.

Tentative QSbiota hh Relevant data for derivation of QS AF

Threshold

Level(1) Tentative QSbiota, hh

Human health

BMDL10 = 9 µg BDE-99.kg-1bw

corresponding to

an internal daily dose of:

4.2 10-3 µg BDE-99.kg-1bw.d-1

30 0.14 10-3

µg.kg-1bw.d-1

8.522 10-3µg.kg-1biota ww

corresponding to

4.9 10-8 µg.l-1

2.4 10-9 µg.l-1 (1)Given that toxico-dynamics differences between experimental animals and humans are already taken on board by the back calculation from BMDL10 to the daily dose of 4.2 10-3 µg.kg-1

bw.d-1, an assessment factor of 30 is deemed sufficient to derive the Threshold Level for human health protection. This is consistent with the recommendations of the REACH guidance: Chapter R.8: Characterisation of dose [concentration]-response for human health (ECHA, 2010).

Given the above considerations on bioaccumulation and biomagnification issues (see section 5.3 and above in section 7.2), and for the same reasons as described in section 7.2, fish should be recommended as the trophic level to monitor when considering BDE congeners (ideally it would even be recommendation of a carnivorous fish).

As regards protection of human health from consumption of drinking water, there are no standard guidelines available. Therefore, a calculated value is proposed to estimate QShh, dw.

Human health via consumption of drinking water Master reference


43

Existing drinking water standard(s) No regulatory standard Directive 98/83/EC

Drinking water standard (calculated) 0.49 10-3 µg.l-1 E.C., 2011


44

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